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Los cúmulos quirales magnéticos 3d-4f que muestran dicroísmo magnetoquiral en el sitio multimetal

Xing Wang¹, Shi-Qiang Wang¹, Jia-Nan Chen¹

¹Collaborative Innovation Center of Chemistry for Energy Materials State Key Laboratory of Physical Chemistry of Solid Surfaces and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.

Journal of the American Chemical Society

|May 3, 2022

Resumen

Los investigadores sintetizaron grupos de metales quirales con estructuras helicoidales. Estos cúmulos {Ln5Ni6} exhiben propiedades magnéticas únicas y muestran intensas señales de dicroísmo magnetoquiral (MChD), revelando información sobre las interacciones entre metales y ligandos.

Área de la Ciencia:

Química de coordinación
Química supramolecular
Magnetoquímica

Sus antecedentes:

Los ligandos quirales son cruciales para crear arquitecturas moleculares asimétricas.
Los grupos de metales de transición de lantánidos ofrecen propiedades magnéticas y ópticas ajustables.
La comprensión de la interacción entre la quiralidad y el magnetismo en los sistemas heterometálicos es un área de investigación activa.

Objetivo del estudio:

Informar sobre el autoensamblaje molecular de nuevos grupos metálicos con puentes de hidróxido {Ln5Ni6}.
Para investigar las propiedades magnéticas y la quiralidad helicoidal de estos grupos heterometálicos 3d-4f.
Explorar los fenómenos de dicroísmo magnetoquiral (MChD) en estos sistemas.

Principales métodos:

Síntesis de clústeres de {Ln5Ni6} utilizando ligandos quirales enantiopuros y precursores metálicos.
Difracción de rayos X de un solo cristal para la caracterización estructural.
Mediciones de la susceptibilidad magnética a la corriente continua.
Espectroscopia de dicroísmo magnetoquiral (MChD), en comparación con el dicroísmo circular natural y magnético.

Principales resultados:

Síntesis exitosa de grupos quirales isostruturales, tipo sándwich, helicoidales (Ln = Dy, Y).
Acoplamiento ferromagnético observado entre los centros DyIII y NiII en {Dy5Ni6}.
Acoplamiento antiferromagnético y/o anisotropía magnética identificados para los centros de NiII en {Y5Ni6}.
Primera observación experimental de señales de MChD de sitios multimetales intensos en la región visible-infrarroja cercana.

Conclusiones:

Las señales MChD en {Dy5Ni6} se atribuyen tanto a la actividad óptica natural (transiciones NiII d-d) como a la actividad óptica magnética (transiciones DyIII f-f).
Este estudio proporciona una nueva plataforma para el diseño de materiales magnéticos quirales.
Los hallazgos ofrecen información fundamental sobre los orígenes de MChD en sistemas heterometálicos complejos.

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